CN104297305B - A kind of CdS sensitization TiO 2environmental estrogens Optical Electro-Chemistry transducer production method and application - Google Patents
A kind of CdS sensitization TiO 2environmental estrogens Optical Electro-Chemistry transducer production method and application Download PDFInfo
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- 229960005309 estradiol Drugs 0.000 claims abstract description 5
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- PROQIPRRNZUXQM-ZXXIGWHRSA-N estriol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H]([C@H](O)C4)O)[C@@H]4[C@@H]3CCC2=C1 PROQIPRRNZUXQM-ZXXIGWHRSA-N 0.000 claims abstract description 5
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- 239000000243 solution Substances 0.000 claims description 90
- 235000019441 ethanol Nutrition 0.000 claims description 35
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 34
- 239000012086 standard solution Substances 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
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- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 230000012447 hatching Effects 0.000 claims description 14
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 5
- 229920002518 Polyallylamine hydrochloride Polymers 0.000 claims description 5
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Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The present invention relates to a kind of CdS sensitization TiO
2environmental estrogens Optical Electro-Chemistry transducer production method and application, the method utilizes TiO
2as antigen capture base material, adopt and directly drip Na
2the method of S, at Cd
2+the TiP nano material of functionalization, as the surface in situ generation CdS photoelectric activity material of label modified electrode, is irradiated CdS by the LED of visible wavelength and is changed into photo-signal.Base material TiO
2matching degree can be with good with CdS, the photocurrent switching signal of CdS can be improved further, thus preparation super sensitivity detection estradiol, estriol, diethylstilbestrol, bisphenol-A, nonylphenol, the competitive type Optical Electro-Chemistry immunosensor of the multiple environmental contaminants such as oestrone.
Description
Technical field
The present invention relates to a kind of CdS sensitization TiO
2environmental estrogens Optical Electro-Chemistry transducer production method and application, be specifically related to a kind of in-situ preparation CdS sensitization TiO
2the preparation method of competitive type environmental estrogens Photoelectrochemistrbiosensor biosensor and application, belong to new function material and environmental contaminants bio-sensing detection technique field.
Background technology
Along with the fast development of modern industrial or agricultural, a large amount of environmentally hazardous substance enters human habitat along with the activity in production of the mankind, produces high risks to the health of the mankind.Environmental estrogens refers to and is present in environment, has the chemical substance of similar biosome inner estrogen activity, can produce the environmental toxin with simulation estrogen action after entering human body.Trace estrogen in environment enters human body by food chain, false hormone being formed, by affecting the endocrinal glands that the body weight for humans such as human adrenal, thyroid gland is wanted, making its abnormal secretion, thus cause nerve system of human body and immune dysfunction, have a strong impact on human physical and mental health.
Monitoring is the important step ensureing food security, sets up a kind of method that is quick, easy, Sensitive Detection environmental estrogens very important.The domestic and international method to environmental estrogens detection mainly contains high performance liquid chromatography, immunological method, electrochemical method, bioanalysis etc. at present, but majority needs expensive instrument, and its complicated operation, detects limit for height, can not well be applied.Therefore, in order to solve the weak point of said method, the invention provides a kind of simple, fast, sensitivity and the high Optical Electro-Chemistry immune analysis method of selectivity.
Optical Electro-Chemistry sensor is the class pick-up unit determining testing concentration based on the light transfer characteristic of material.Optical Electro-Chemistry detection method have highly sensitive, equipment simple, be easy to microminiaturized feature, become a kind of analytical approach having application potential, had broad application prospects in food, environment, medicine and other fields.
The present invention adopts the rhodamine B-sensitized TiO with good efficiency of light absorption
2semiconductor composite catches substrate as haptens, utilizes Cd
2+the porous TiP nanoparticle label antibody of functionalization, by directly dripping Na at electrode surface
2s, the narrow band gap CdS of in-situ preparation high optoelectronic conversion ratio.Due to base material TiO
2matching degree can be with good with CdS, the photocurrent switching signal of CdS can be improved further.A kind of CdS sensitization TiO prepared by the present invention
2environmental estrogens Optical Electro-Chemistry sensor, there is low cost, highly sensitive, specificity good, the advantage such as quick detection, and preparation process is simple, achieves quick, the Sensitive Detection to multiple environmental estrogens, effectively overcome the deficiency of current environmental estrogens detection method in visible region.
Summary of the invention
An object of the present invention is based on in-situ preparation narrow band gap CdS, constructs a kind of simple, quick, sensitive competitive type Optical Electro-Chemistry immunosensor.
Two of object of the present invention is by generated in-situ narrow band gap CdS and substrate broad-band gap TiO
2can mate by band, achieve quick, the Sensitive Detection object of visible region to multiple environmental estrogens.
technical scheme of the present invention is as follows:
1. a CdS sensitization TiO2 environmental estrogens Optical Electro-Chemistry transducer production method, is characterized in that, comprise the following steps:
(1) electro-conductive glass is used successively acetone, ethanol and ultrapure water ultrasonic cleaning, nitrogen dries up; Get 6 μ L, 2 ~ 4mg/mL rhodamine B functionalization TiO
2solution is added drop-wise to the conducting surface of electro-conductive glass, dries under room temperature, and 400 ~ 500 DEG C of calcining 30 ~ 60min, cooling, obtains rhodamine B-TiO
2the glass electrode of modifying;
(2) at rhodamine B-TiO
2the glass electrode surface modified, drips the environmental estrogens standard solution of 4 μ L, 0.1 ~ 1 μ g/mL, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
(3) continue dropping 4 μ L, massfraction be 1 ~ 3% BSA solution, enclosed-electrode is nonspecific activity site on the surface, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
(4) continuation dropping 4 μ L environmental estrogens standard solution and antibody hatch the mixed liquor of solution, and ultrapure water electrode surface, dries in 4 DEG C of refrigerators, has obtained CdS sensitization TiO
2optical Electro-Chemistry sensor.
Described environmental estrogens standard solution and antibody hatch the mixed liquor of solution, are by isopyknic TiPCd
2+-Ab antibody is hatched solution environmental estrogens standard solution to be measured with variable concentrations respectively and is mixed obtained; The environmental estrogens standard solution that described variable concentrations is to be measured, its concentration is 1pg/mL ~ 20ng/mL.
2. rhodamine B functionalization TiO
2the preparation of solution
(1) TiO
2the preparation of powder
0.01 ~ 0.03mol butyl titanate is dissolved in 30mL ethanol, adds 10mL water, stirs 30 ~ 120min, mixed solution is transferred in autoclave, react 5 ~ 10h at 200 DEG C, the product distilled water obtained and absolute ethyl alcohol centrifuge washing, vacuum drying 12h under 70 ~ 90 DEG C of conditions, obtains TiO
2powder;
(2) rhodamine B functionalization TiO
2the preparation of solution
Get 10mgTiO
2powder joins in 2.5mL, 0.1 ~ 0.2mg/mL rhodamine B aqueous solution, regulates pH to 7 with 0.1mol/LNaOH, and vibration 4 ~ 24h, centrifugal drying, is made into the rhodamine B functionalization TiO of 2mg/mL with water
2solution.
3.TiPCd
2+the preparation of-Ab antibody hatching solution
(1) preparation of TiP
The lauryl sodium sulfate of 0.3g adds 20mL EtOH Sonicate, adds 2 ~ 4mL, massfraction is the H of 85% in solution
3pO
4, mixed solution stirs 4h, generates the NaH of white
2pO
4precipitation, Centrifugal dispersion is in a small amount of ethanol; The mixed solution of 5mL butyl titanate and ethanol is added fast in the solution that above-mentioned ethanol disperses, in this miscible fluid, the volume ratio of butyl titanate and ethanol is 1:4 ~ 8, stirs 20min, 80 DEG C of backflow 6h, with water, each centrifuge washing of ethanol three times, obtain TiP white powder;
(2) TiPCd
2+the preparation of solution
By the Cd (NO of 1mL, 40mg/mLTiP aqueous solution and 17mL, 6 ~ 14mmol/L
3)
24H
2o aqueous solution is blended, stirs 4 ~ 24h at 50 DEG C, centrifugal, water washing 3 times, the TiPCd obtained
2+be the TiPCd of 20mg/mL with aqueous dispersion
2+solution;
(3) TiPCd
2+the preparation of-Ab antibody hatching solution
To the TiPCd of 2mL, 20mg/mL
2+the polyallylamine hydrochloride aqueous solution of 7.5mL, 1 ~ 3mg/mL is added, ultrasonic 20 ~ 60min, centrifuge washing in solution; Be dispersed in 2mL, massfraction is in the glutaraldehyde water solution of 1.0 ~ 3.5%, concussion 2h is also centrifugal, is 2mL with the PBS dilution that pH is 7.4; Add 10 ~ 100 μ L, 1mg/mL environmental estrogens antibody A b solution, vibration 20h, be the PBS centrifuge washing of 7.4 with pH, being finally dispersed in 5mL, pH is in the PBS of 7.4, obtained TiPCd
2+-Ab antibody hatching solution, saves backup at 4 DEG C.
4. the detecting step of environmental estrogens
(1) at prepared Optical Electro-Chemistry sensor electrode surface, the Na of 4 μ L, 0.7mol/L is dripped
2s solution, places 30 ~ 80min;
(2) electrochemical workstation is used to test with three-electrode system, saturated calomel electrode is contrast electrode, platinum electrode is auxiliary electrode, prepared Optical Electro-Chemistry sensor electrical very working electrode, tested in containing in the PBS buffer solution of 0.1mol/L ascorbic acid of 10mL, pH7.0 ~ 7.5;
(3) used time m-current method to environmental stimulus element standard solution detect, arranging voltage is 0.1V, working time 100s, irradiation LED lamp wavelength is 400 ~ 450nm;
(4) after background current tends towards stability, to turn on light prolonged exposure 10s every 20s, recording light electric current, drawing curve;
(5) environmental estrogens standard solution is replaced to detect environmental estrogens sample solution to be measured.
5. environmental estrogens of the present invention is selected from one of following: estradiol, estriol, diethylstilbestrol, bisphenol-A, nonylphenol, oestrone.
useful achievement of the present invention
(1) with simple TiO
2compare, adopt rhodamine B functionalization TiO
2, effectively can improve photoelectric transformation efficiency.
(2) Cd is utilized
2+the TiP nano particle of functionalization is labeled thing as antibody, adopts and directly drips Na at electrode surface
2the CdS semiconductor nano material of S in-situ preparation narrow band gap, raw material is cheap, method is simple.
(3) the generated in-situ CdS of electrode surface with as the TiO catching base material
2have and good can be with coupling, effectively raise the photoelectric transformation efficiency of CdS, obtained sensor achieves the super sensitivity detection to environmental estrogens.
(5) the present invention utilizes the immune response of haptens, antibody, improves the specificity of detection method.
(6) the competitive type Optical Electro-Chemistry immunosensor prepared of the present invention, for the detection of multiple environmental estrogens, the response time is short, and detectability is low, and the range of linearity is wide, can realize simple, quick, highly sensitive and specific detection.
Embodiment
embodiment 1a kind of CdS sensitization TiO2 environmental estrogens Optical Electro-Chemistry transducer production method and application
(1) electro-conductive glass is used successively acetone, ethanol and ultrapure water ultrasonic cleaning, nitrogen dries up; Get 6 μ L, 2mg/mL rhodamine B functionalization TiO
2solution is added drop-wise to the conducting surface of electro-conductive glass, dries under room temperature, and 400 DEG C of calcining 30min, cooling, obtains rhodamine B-TiO
2the glass electrode of modifying;
(2) at rhodamine B-TiO
2the glass electrode surface modified, drips the environmental estrogens standard solution of 4 μ L, 0.1 μ g/mL, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
(3) continue dropping 4 μ L, massfraction be 1% BSA solution, enclosed-electrode is nonspecific activity site on the surface, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
(4) continuation dropping 4 μ L environmental estrogens standard solution and antibody hatch the mixed liquor of solution, and ultrapure water electrode surface, dries in 4 DEG C of refrigerators, has obtained CdS sensitization TiO
2optical Electro-Chemistry sensor.
Described environmental estrogens standard solution and antibody hatch the mixed liquor of solution, are by isopyknic TiPCd
2+-Ab antibody is hatched solution environmental estrogens standard solution to be measured with variable concentrations respectively and is mixed obtained; The environmental estrogens standard solution that described variable concentrations is to be measured, its concentration is 1pg/mL ~ 20ng/mL.
embodiment 2a kind of CdS sensitization TiO2 environmental estrogens Optical Electro-Chemistry transducer production method and application
(1) electro-conductive glass is used successively acetone, ethanol and ultrapure water ultrasonic cleaning, nitrogen dries up; Get 6 μ L, 3mg/mL rhodamine B functionalization TiO
2solution is added drop-wise to the conducting surface of electro-conductive glass, dries under room temperature, and 450 DEG C of calcining 45min, cooling, obtains rhodamine B-TiO
2the glass electrode of modifying;
(2) at rhodamine B-TiO
2the glass electrode surface modified, drips the environmental estrogens standard solution of 4 μ L, 0.5 μ g/mL, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
(3) continue dropping 4 μ L, massfraction be 2% BSA solution, enclosed-electrode is nonspecific activity site on the surface, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
(4) continuation dropping 4 μ L environmental estrogens standard solution and antibody hatch the mixed liquor of solution, and ultrapure water electrode surface, dries in 4 DEG C of refrigerators, has obtained CdS sensitization TiO
2optical Electro-Chemistry sensor.
Described environmental estrogens standard solution and antibody hatch the mixed liquor of solution, are by isopyknic TiPCd
2+-Ab antibody is hatched solution environmental estrogens standard solution to be measured with variable concentrations respectively and is mixed obtained; The environmental estrogens standard solution that described variable concentrations is to be measured, its concentration is 1pg/mL ~ 20ng/mL.
embodiment 3a kind of CdS sensitization TiO2 environmental estrogens Optical Electro-Chemistry transducer production method and application
(1) electro-conductive glass is used successively acetone, ethanol and ultrapure water ultrasonic cleaning, nitrogen dries up; Get 6 μ L, 4mg/mL rhodamine B functionalization TiO
2solution is added drop-wise to the conducting surface of electro-conductive glass, dries under room temperature, and 500 DEG C of calcining 60min, cooling, obtains rhodamine B-TiO
2the glass electrode of modifying;
(2) at rhodamine B-TiO
2the glass electrode surface modified, drips the environmental estrogens standard solution of 4 μ L, 1 μ g/mL, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
(3) continue dropping 4 μ L, massfraction be 3% BSA solution, enclosed-electrode is nonspecific activity site on the surface, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
(4) continuation dropping 4 μ L environmental estrogens standard solution and antibody hatch the mixed liquor of solution, and ultrapure water electrode surface, dries in 4 DEG C of refrigerators, has obtained CdS sensitization TiO
2optical Electro-Chemistry sensor.
Described environmental estrogens standard solution and antibody hatch the mixed liquor of solution, are by isopyknic TiPCd
2+-Ab antibody is hatched solution environmental estrogens standard solution to be measured with variable concentrations respectively and is mixed obtained; The environmental estrogens standard solution that described variable concentrations is to be measured, its concentration is 1pg/mL ~ 20ng/mL.
embodiment 4rhodamine B functionalization TiO
2the preparation of solution
(1) TiO
2the preparation of powder
0.01mol butyl titanate is dissolved in 30mL ethanol, adds 10mL water, stirs 30min, mixed solution is transferred in autoclave, at 200 DEG C, react 5h, the product distilled water obtained and absolute ethyl alcohol centrifuge washing, vacuum drying 12h under 70 DEG C of conditions, obtains TiO
2powder;
(2) rhodamine B functionalization TiO
2the preparation of solution
Get 10mgTiO
2powder joins in 2.5mL, 0.1mg/mL rhodamine B aqueous solution, regulates pH to 7 with 0.1mol/LNaOH, and vibration 4h, centrifugal drying, is made into the rhodamine B functionalization TiO of 2mg/mL with water
2solution.
Embodiment 5 rhodamine B functionalization TiO
2the preparation of solution
(1) TiO
2the preparation of powder
0.02mol butyl titanate is dissolved in 30mL ethanol, adds 10mL water, stirs 60min, mixed solution is transferred in autoclave, at 200 DEG C, react 8h, the product distilled water obtained and absolute ethyl alcohol centrifuge washing, vacuum drying 12h under 80 DEG C of conditions, obtains TiO
2powder;
(2) rhodamine B functionalization TiO
2the preparation of solution
Get 10mgTiO
2powder joins in 2.5mL, 0.15mg/mL rhodamine B aqueous solution, regulates pH to 7 with 0.1mol/LNaOH, and vibration 10h, centrifugal drying, is made into the rhodamine B functionalization TiO of 2mg/mL with water
2solution.
embodiment 6rhodamine B functionalization TiO
2the preparation of solution
(1) TiO
2the preparation of powder
0.03mol butyl titanate is dissolved in 30mL ethanol, adds 10mL water, stirs 120min, mixed solution is transferred in autoclave, at 200 DEG C, react 10h, the product distilled water obtained and absolute ethyl alcohol centrifuge washing, vacuum drying 12h under 90 DEG C of conditions, obtains TiO
2powder;
(2) rhodamine B functionalization TiO
2the preparation of solution
Get 10mgTiO
2powder joins in 2.5mL, 0.2mg/mL rhodamine B aqueous solution, regulates pH to 7 with 0.1mol/LNaOH, and vibration 24h, centrifugal drying, is made into the rhodamine B functionalization TiO of 2mg/mL with water
2solution.
embodiment 7tiPCd
2+the preparation of-Ab antibody hatching solution
(1) preparation of TiP
The lauryl sodium sulfate of 0.3g adds 20mL EtOH Sonicate, adds 2mL, massfraction is the H of 85% in solution
3pO
4, mixed solution stirs 4h, generates the NaH of white
2pO
4precipitation, Centrifugal dispersion is in a small amount of ethanol; In the solution that above-mentioned ethanol disperses, add the mixed solution of 5mL butyl titanate and ethanol fast, in this miscible fluid, the volume ratio of butyl titanate and ethanol is 1:4, stirs 20min, and 80 DEG C of backflow 6h, with water, each centrifuge washing of ethanol three times, obtain TiP white powder;
(2) TiPCd
2+the preparation of solution
By the Cd (NO of 1mL, 40mg/mLTiP aqueous solution and 17mL, 6 ~ 14mol/L
3)
24H
2o aqueous solution is blended, stirs 4h at 50 DEG C, centrifugal, water washing 3 times, the TiPCd obtained
2+be the TiPCd of 20mg/mL with aqueous dispersion
2+solution;
(3) TiPCd
2+the preparation of-Ab antibody hatching solution
To the TiPCd of 2mL, 20mg/mL
2+the polyallylamine hydrochloride aqueous solution of 7.5mL, 1mg/mL is added, ultrasonic 20min, centrifuge washing in solution; Be dispersed in 2mL, massfraction is in the glutaraldehyde water solution of 1.0%, concussion 2h is also centrifugal, is 2mL with the PBS dilution that pH is 7.4; Add 10 μ L, 1mg/mL environmental estrogens antibody A b solution, vibration 20h, be the PBS centrifuge washing of 7.4 with pH, being finally dispersed in 5mL, pH is in the PBS of 7.4, obtained TiPCd
2+-Ab antibody hatching solution, saves backup at 4 DEG C.
embodiment 8tiPCd
2+the preparation of-Ab antibody hatching solution
(1) preparation of TiP
The lauryl sodium sulfate of 0.3g adds 20mL EtOH Sonicate, adds 3mL, massfraction is the H of 85% in solution
3pO
4, mixed solution stirs 4h, generates the NaH of white
2pO
4precipitation, Centrifugal dispersion is in a small amount of ethanol; In the solution that above-mentioned ethanol disperses, add the mixed solution of 5mL butyl titanate and ethanol fast, in this miscible fluid, the volume ratio of butyl titanate and ethanol is 1:6, stirs 20min, and 80 DEG C of backflow 6h, with water, each centrifuge washing of ethanol three times, obtain TiP white powder;
(2) TiPCd
2+the preparation of solution
By the Cd (NO of 1mL, 40mg/mLTiP aqueous solution and 17mL, 10mmol/L
3)
24H
2o aqueous solution is blended, stirs 20h at 50 DEG C, centrifugal, water washing 3 times, the TiPCd obtained
2+be the TiPCd of 20mg/mL with aqueous dispersion
2+solution;
(3) TiPCd
2+the preparation of-Ab antibody hatching solution
To the TiPCd of 2mL, 20mg/mL
2+the polyallylamine hydrochloride aqueous solution of 7.5mL, 2mg/mL is added, ultrasonic 45min, centrifuge washing in solution; Be dispersed in 2mL, massfraction is in the glutaraldehyde water solution of 2.0%, concussion 2h is also centrifugal, is 2mL with the PBS dilution that pH is 7.4; Add 50 μ L, 1mg/mL environmental estrogens antibody A b solution, vibration 20h, be the PBS centrifuge washing of 7.4 with pH, being finally dispersed in 5mL, pH is in the PBS of 7.4, obtained TiPCd
2+-Ab antibody hatching solution, saves backup at 4 DEG C.
embodiment 9tiPCd
2+the preparation of-Ab antibody hatching solution, step is as follows:
(1) preparation of TiP
The lauryl sodium sulfate of 0.3g adds 20mL EtOH Sonicate, adds 4mL, massfraction is the H of 85% in solution
3pO
4, mixed solution stirs 4h, generates the NaH of white
2pO
4precipitation, Centrifugal dispersion is in a small amount of ethanol; In the solution that above-mentioned ethanol disperses, add the mixed solution of 5mL butyl titanate and ethanol fast, in this miscible fluid, the volume ratio of butyl titanate and ethanol is 1:8, stirs 20min, and 80 DEG C of backflow 6h, with water, each centrifuge washing of ethanol three times, obtain TiP white powder;
(2) TiPCd
2+the preparation of solution
By the Cd (NO of 1mL, 40mg/mLTiP aqueous solution and 17mL, 14mmol/L
3)
24H
2o aqueous solution is blended, stirs 24h at 50 DEG C, centrifugal, water washing 3 times, the TiPCd obtained
2+be the TiPCd of 20mg/mL with aqueous dispersion
2+solution;
(3) TiPCd
2+the preparation of-Ab antibody hatching solution
To the TiPCd of 2mL, 20mg/mL
2+the polyallylamine hydrochloride aqueous solution of 7.5mL, 3mg/mL is added, ultrasonic 60min, centrifuge washing in solution; Be dispersed in 2mL, massfraction is in the glutaraldehyde water solution of 3.5%, concussion 2h is also centrifugal, is 2mL with the PBS dilution that pH is 7.4; Add 100 μ L, 1mg/mL environmental estrogens antibody A b solution, vibration 20h, be the PBS centrifuge washing of 7.4 with pH, being finally dispersed in 5mL, pH is in the PBS of 7.4, obtained TiPCd
2+-Ab antibody hatching solution, saves backup at 4 DEG C.
embodiment 10the detection of estradiol
(1) at prepared Optical Electro-Chemistry sensor electrode surface, the Na of 4 μ L, 0.7mol/L is dripped
2s solution, places 30 ~ 80min;
(2) electrochemical workstation is used to test with three-electrode system, saturated calomel electrode is contrast electrode, platinum electrode is auxiliary electrode, prepared Optical Electro-Chemistry sensor electrical very working electrode, tested in containing in the PBS buffer solution of 0.1mol/L ascorbic acid of 10mL, pH7.0 ~ 7.5;
(3) used time m-current method detects analysis thing standard solution, and arranging voltage is 0.1V, working time 100s, irradiation LED lamp wavelength is 400 ~ 450nm;
(4) after background current tends towards stability, to turn on light prolonged exposure 10s every 20s, recording light electric current, drawing curve;
(5) carry out estradiol sample analysis according to the method for drawing curve, recording the range of linearity is 5pg/mL ~ 10ng/mL, detects and is limited to 2pg/mL.
embodiment 11the detection of estriol
Drawing curve step, with embodiment 10, carries out estriol sample analysis according to the method for drawing curve, and recording the range of linearity is 1.5pg/mL ~ 10ng/mL, detects and is limited to 0.85pg/mL.
embodiment 12the detection of diethylstilbestrol
Drawing curve step, with embodiment 10, carries out diethylstilbestrol sample analysis according to the method for drawing curve, and recording the range of linearity is 7.5pg/mL ~ 13ng/mL, detects and is limited to 2.3pg/mL.
embodiment 13the detection of bisphenol-A
Drawing curve step, with embodiment 10, carries out bisphenol-A sample analysis according to the method for drawing curve, and recording the range of linearity is 5pg/mL ~ 8ng/mL, detects and is limited to 1.5pg/mL.
embodiment 14the detection of nonylphenol
Drawing curve step, with embodiment 10, carries out nonylphenol sample analysis according to the method for drawing curve, and recording the range of linearity is 10pg/mL ~ 20ng/mL, detects and is limited to 2.8pg/mL.
embodiment 14the detection of oestrone
Drawing curve step, with embodiment 10, carries out oestrone sample analysis according to the method for drawing curve, and recording the range of linearity is 8pg/mL ~ 18ng/mL, detects and is limited to 1.8pg/mL.
Claims (2)
1. a CdS sensitization TiO
2environmental estrogens Optical Electro-Chemistry transducer production method, is characterized in that, comprise the following steps:
(1) rhodamine B functionalization TiO
2the preparation of solution
1) 0.01 ~ 0.03mol butyl titanate is dissolved in 30mL ethanol, add 10mL water, stir 30 ~ 120min, mixed solution is transferred in autoclave, 5 ~ 10h is reacted at 200 DEG C, the product distilled water obtained and absolute ethyl alcohol centrifuge washing, vacuum drying 12h under 70 ~ 90 DEG C of conditions, obtains TiO
2powder;
2) 10mgTiO is got
2powder joins in 2.5mL, 0.1 ~ 0.2mg/mL rhodamine B aqueous solution, regulates pH to 7 with 0.1mol/LNaOH, and vibration 4 ~ 24h, centrifugal drying, is made into the rhodamine B functionalization TiO of 2mg/mL with water
2solution;
(2) TiPCd
2+the preparation of-Ab antibody hatching solution
1) lauryl sodium sulfate of 0.3g adds 20mL EtOH Sonicate, adds 2 ~ 4mL, massfraction is the H of 85% in solution
3pO
4, mixed solution stirs 4h, generates the NaH of white
2pO
4precipitation, Centrifugal dispersion is in a small amount of ethanol; The mixed solution of 5mL butyl titanate and ethanol is added fast in the solution that above-mentioned ethanol disperses, in this miscible fluid, the volume ratio of butyl titanate and ethanol is 1:4 ~ 8, stirs 20min, 80 DEG C of backflow 6h, with water, each centrifuge washing of ethanol three times, obtain TiP white powder;
2) by the Cd (NO of 1mL, 40mg/mLTiP aqueous solution and 17mL, 6 ~ 14mmol/L
3)
24H
2o aqueous solution is blended, stirs 4 ~ 24h at 50 DEG C, centrifugal, water washing 3 times, the TiPCd obtained
2+be the TiPCd of 20mg/mL with aqueous dispersion
2+solution;
3) to the TiPCd of 2mL, 20mg/mL
2+the polyallylamine hydrochloride aqueous solution of 7.5mL, 1 ~ 3mg/mL is added, ultrasonic 20 ~ 60min, centrifuge washing in solution; Be dispersed in 2mL, massfraction is in the glutaraldehyde water solution of 1.0 ~ 3.5%, concussion 2h is also centrifugal, is 2mL with the PBS dilution that pH is 7.4; Add 10 ~ 100 μ L, 1mg/mL environmental estrogens antibody A b solution, vibration 20h, be the PBS centrifuge washing of 7.4 with pH, being finally dispersed in 5mL, pH is in the PBS of 7.4, obtained TiPCd
2+-Ab antibody hatching solution, saves backup at 4 DEG C;
(3) preparation of sensor
1) electro-conductive glass is used successively acetone, ethanol and ultrapure water ultrasonic cleaning, nitrogen dries up; Get 6 μ L, 2 ~ 4mg/mL rhodamine B functionalization TiO
2solution is added drop-wise to the conducting surface of electro-conductive glass, dries under room temperature, and 400 ~ 500 DEG C of calcining 30 ~ 60min, cooling, obtains rhodamine B-TiO
2the glass electrode of modifying;
2) at rhodamine B-TiO
2the glass electrode surface modified, drips the environmental estrogens standard solution of 4 μ L, 0.1 ~ 1 μ g/mL, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
3) continue dropping 4 μ L, massfraction be 1 ~ 3% BSA solution, enclosed-electrode is nonspecific activity site on the surface, ultrapure water electrode surface, dries in 4 DEG C of refrigerators;
4) continuation dropping 4 μ L environmental estrogens standard solution and antibody hatch the mixed liquor of solution, and ultrapure water electrode surface, dries in 4 DEG C of refrigerators, has obtained CdS sensitization TiO
2optical Electro-Chemistry sensor;
Described environmental estrogens standard solution and antibody hatch the mixed liquor of solution, are by isopyknic TiPCd
2+-Ab antibody is hatched solution environmental estrogens standard solution to be measured with variable concentrations respectively and is mixed obtained;
The environmental estrogens standard solution that described variable concentrations is to be measured, its concentration is 1pg/mL ~ 20ng/mL.
2. the sensor prepared of preparation method as claimed in claim 1 is for the detection of environmental estrogens, and it is characterized in that, step is as follows:
(1) at prepared Optical Electro-Chemistry sensor electrode surface, the Na of 4 μ L, 0.7mol/L is dripped
2s solution, places 30 ~ 80min;
(2) electrochemical workstation is used to test with three-electrode system, saturated calomel electrode is contrast electrode, platinum electrode is auxiliary electrode, prepared Optical Electro-Chemistry sensor electrical very working electrode, tested in containing in the PBS buffer solution of 0.1mol/L ascorbic acid of 10mL, pH7.0 ~ 7.5;
(3) m-current method detects environmental estrogens standard solution the used time, and arranging voltage is 0.1V, working time 100s, irradiation LED lamp wavelength is 400 ~ 450nm;
(4) after background current tends towards stability, to turn on light prolonged exposure 10s, then recording light electric current every 20s, drawing curve;
(5) environmental estrogens standard solution is replaced to detect environmental estrogens sample solution to be measured;
Described ambient environment estrogen is selected from one of following: estradiol, estriol, diethylstilbestrol, bisphenol-A, nonylphenol, oestrone.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103235144A (en) * | 2013-04-19 | 2013-08-07 | 济南大学 | Preparation method and application of sensor for simultaneously detecting two environmental estrogens |
| CN103920504A (en) * | 2014-04-18 | 2014-07-16 | 中国石油大学(华东) | Preparation and application of dendriform TiO2-coating CdS hollow double-shell material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101273600B1 (en) * | 2011-04-13 | 2013-06-11 | 한국과학기술원 | Method for Photochemical Regenerating Oxidoreductase Cofactor Using Nanotubular Metal Oxide-Inorganic Photosensitizer Complex |
-
2014
- 2014-09-06 CN CN201410451336.XA patent/CN104297305B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103235144A (en) * | 2013-04-19 | 2013-08-07 | 济南大学 | Preparation method and application of sensor for simultaneously detecting two environmental estrogens |
| CN103920504A (en) * | 2014-04-18 | 2014-07-16 | 中国石油大学(华东) | Preparation and application of dendriform TiO2-coating CdS hollow double-shell material |
Non-Patent Citations (1)
| Title |
|---|
| 前处理对CdS敏化TiO2纳晶复合半导体电极光电化学性能的影响";王美容，贾建光;《北京化工大学学报》;20070131;第34卷(第1期);85-88 * |
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